This invention pertains to silicone resin based composites. More specifically, this invention relates to fiber reinforced, resin composites having a rigid silicone matrix resin where the composite layers are interleaved with a thin silicone layer of compliant impact resistant material.
Fiber reinforced, silicone matrix resin composites find many applications in structural components. The fiber reinforcement often takes the form of woven glass fiber mats. Woven carbon fiber mats offer a higher modulus reinforcing media but they are more expensive than glass fibers. Other fiber compositions such as aramid, nylon, polyester and quartz fibers may be used. Other fibrous forms, such as non-woven mats and layers of loose fibers, may also be used in silicone resin based composite applications.
A large family of silicone matrix resins are available for composite applications. Such resins are typically highly branched and cross-linked polymer molecules in cured form. They are substantially rigid materials displaying a high modulus of elasticity and high elastic shear modulus.
These fiber reinforced, silicone matrix resin composites in multi-layer laminated form are strong and fire resistant and find applications such as interiors for airplanes and ships. They are also used in electrical applications, such as wiring boards and printed circuit boards, requiring flexural strength and low weight.
Thus, laminated silicone resin composites have many uses. However, when they are stressed to failure, such composites tend to fail by delamination. The fracture occurs in the matrix resin between layers of reinforcing fibers. It would be desirable to devise a fiber reinforced, silicone composite more resistant to such a failure mode. Therefore, it is an object of this invention to provide an improved silicone resin based, laminated composite displaying higher toughness and impact resistance.
This invention improves the fabrication of rigid silicone matrix resin, fiber mat reinforced composites by incorporating a thin layer of tough compliant silicone resin at the laminar interfaces. As successive layers of matrix resin wetted fiber mats are laid up, a thin coating of a suitable mobile silicone resin, formulated for its toughness relative to the silicone matrix resin, is applied between the layers. Preferably, the mobile silicone resin is sprayed onto one side of each wetted fiber layer. The viscosity of the interleaved, or interfacial resin coating permits it to flow and conform to the surface details of the resin impregnated glass fiber mat, for example, and provide a substantially void-free layer between the laminations. Preferably, the interleaved silicone resin is formulated to cure during the curing of the matrix resin in the fabricated laminar structure.
Suitable silicone resin matrices of the composites are curable copolymers that are produced, for example, from a combination of traditional siloxane di-functional and tri-functional building blocks. These blocks include PhSiO3/2, MeSiO3/2, PhMeSiO2/2, Me2SiO2/2, ViMeSiO2/2, HMeSiO2/2, HPhSiO2/2, ViSiO3/2, ViMe2SiO1/2, O1/2(Me2)Sixe2x80x94Rxe2x80x94Si(Me2)O1/2, and the like. Here Ph represents the phenyl group, Me represents the methyl group, Vi the vinyl group and R a divalent hydrocarbon, such as the phenylene group. An example of a suitable matrix resin for woven glass fiber mats is the silanol group containing (PhSiO3/2)0.40(MeSiO3/2)0.45(Ph2SiO2/2)0.1(PhMeSiO2/2)0.05. The content of trifunctional blocks is such that the matrix silicone resin is substantially rigid upon curing, typically having a Young""s Modulus greater than or equal to 0.67 GPa. Other suitable polymer building blocks include silphenylenes, silmethylenes, silethylenes and the like. The silicone matrix resins may include modifiers such as linear or branched silicone segments that add desired physical property benefits to the matrix.
The fiber component of the composites will usually be glass or carbon because of favorable cost and availability, but other fiber reinforcing materials are suitable for many applications. For example, quartz fibers and aramid, nylon and polyester fibers may be used. Woven fiberglass mats are usually preferred for ordinary applications where cost is an important consideration. Non-woven fiber mats and loose fiber layers are suitable.
The silicone resin selected for the interleaf material is to be complementary in its properties to the matrix resin. It is more compliant than the generally rigid matrix resin. The interleaf resin may be synthesized from similar siloxane moieties but the resultant resin is to add toughness, resistance to delamination, and impact strength to the composite. Thus, the interleaf resin will typically contain a smaller portion of trifunctional siloxane groups than the matrix resin and will have a lower Young""s modulus, preferably less than or equal to 0.3 GPa. An example of an interleaf silicone resin for use in combination with the above stated matrix resin is the methoxy functional (PhSiO3/2)0.34(Me2SiO3/2)0.56(MeSiO3/2)0.1 resin. It is preferred that the interleaf resin be applied as a thin compliant film between prepreg laminates and cured simultaneously with the matrix resin.
In most applications, the thickness of a single layer of matrix resin wetted fiber mat is about three to one hundred fifty mils (about 75 to 3750 micrometers). The thickness of the interleaved resin is suitably much smaller, about 25 to 75 micrometers. In general, the thickness of the prepreg will be from three to fifty times the thickness of the interleaf resin layer. Thus, prior art silicone resin laminates comprise a predetermined number of stacked and molded layers of matrix resin impregnated fiber layers. But the laminates of this invention include a relatively thin coating of interleaved silicone resin between each layer of prepreg.
The mechanical properties of composites made with a suitable interleaf resin show higher toughness, without undue loss of strength and modulus, than the analogous composites fabricated without the interleaf silicone resin. Preferably, the interleaf resin causes no loss of heat stability or elevated temperature properties of the composites. The flexural modulus of composites made with and without the interleaf resin are comparable.
Other objects and advantages of the invention will become apparent from a detailed description of preferred examples that follow.
The practice of this invention includes the selection of a suitable silicone matrix resin, a suitable complementary silicone interleaf resin and fibrous reinforcement.
The fibrous reinforcing material is, of course, essential for the composite structure but it is not necessarily a critical part of use of the invention. Woven mats of glass fibers or carbon fibers impart good strength to composites and the woven structures are easy to impregnate with the matrix resin precursor and coat with the interleaf resin precursor. Other forms and fiber compositions may be used without changing the basic strategy of the invention.
The selection of the silicone matrix resin is largely based on known considerations for achieving compatibility with the specified reinforcing fibers and the desired properties of the composite. However, the interleaf silicone resin is chosen for its compatibility with the matrix resin and the requirement that the interleaf resin toughen the composite. Typically each fiber reinforcement layer will be wetted and infiltrated with the matrix resin in a relatively low molecular weight uncured state. This precursor resin material will be suitably formulated so that it is curable by application of heat and pressure to laid up prepreg sheets. Similarly, the precursor form of the interleaf resin will preferably be applied by spraying or other coating step to at least one side of the prepreg strips. Accordingly, it is preferred that both the matrix resin and the tougher interleaf resin be cured at the same time.
As disclosed above, both the matrix resin and interleaf resin will likely contain siloxane groups or blocks like PhSiO3/2, MeSiO3/2, PhMeSiO2/2, Me2SiO2/2, ViMeSiO2/2, HMeSiO2/2, HPhSiO2/2, ViSiO3/2ViMe2SiO1/2, and O1/2(Me2)Sixe2x80x94Rxe2x80x94Si(Me2)O1/2. The uncured form of the resin may contain silanol groups or alkoxy groups so as to be curable by a condensation process. Or the precursor resins may contain functional groups that permit curing by a hydrosilylation reaction
Included among the latter group of suitable silicone matrix resins are the silsesquioxane resins described in U.S. Pat. No. 6,310,146, Katsoulis, et al, entitled Silsesquioxane Resin With High Strength and Fracture Toughness and Method for the Preparation Thereof. The specification of the ""146 patent is incorporated into this specification for a full description of these useful silicone resins.
As taught in the ""146 patent the base silsesquioxane resin is a hydrosilylation reaction curable copolymer resin. It comprises units that have the empirical formula R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2, where a is zero or a positive number, b is zero or a positive number, and c is zero or a positive number, providing that 0.8xe2x89xa6(a+b+c)xe2x89xa63.0. Further, each copolymer has at least two R1 groups per molecule, and each R1 is a functional group independently selected from the group consisting of hydrogen atoms and monovalent hydrocarbon groups having aliphatic unsaturation. Each R2 and R3 are monovalent hydrocarbon groups independently selected from the group consisting of nonfunctional groups and R1.
Preferably, R1 is an alkenyl group such as vinyl or allyl. Typically, R2 and R3 are nonfunctional groups selected from the group consisting of alkyl and aryl groups. Suitable alkyl groups include methyl, ethyl, isopropyl, n-butyl and isobutyl groups. The phenyl group is a typical aryl group. In addition to the other silsesquioxane copolymers identified in this specification, another suitable silsesquioxane copolymer is (PhSiO3/2)0.75(ViMe2SiO1/2)0.25.